Azo dyes and process of making the same.



OTEO WHMIDT, OF MANHHEIM, GERMANY, ASSTGNGR TO BADISGHE ANILIN &'SO 3DA 'EABRIgK, LUDWIG-SHAFEN-ON-THE-RHINE, GERMANY, A CORPORATION.

A20 EYES AND PBDGiESS 0F MAKING THE SAME.

No Drawing.

To all whom it may concern;

Be it known that I, OTTO SCHMIDT, subject of the King of Prussia, residing at Mannheim, Germany, have invented new and useful Im Movements in Dyes and Processes of airing. the Same, of which the following is a specification.

I- lea-ye discovered that I can obtain azo coloring matters which are eminently suitedfor use the form of their lakes by combining a negati-nely substituteddiazo com.- pound with 1.3-diketo-hydro-inden and instead .of 1.3diketo.-hydro-inden, derivatives thereof may be employed. If the diketo-hydrorindcn compound be employed in the form of its carboxylic acid, contain ing the carboxylic acid group in the cyclopentene ring, the carboxyl-ic acid compound of the coloring matter is ,at first produced, the carboxyilic acid group is, however, split off in the presence of acid, giving rise to the diketo-hydro-inde n coloring matter. If a carboxylic acid ester of the diketohydro-inden be employed, the rrespond ing carboxylic acid ester of the coloring matter is at first produced, and this can be transformed into the non-carboxylaited col,-

oring matter by treatment with a saponifying agent. As instances of negatively snbstituted .diazo compounds which can he used according to my invention, I mention those derived from the l-litra-nl-lms, chloranilins, a'niliqnesnlfonie acids, ehlor-ni.traniline, the corresponding naph-t-h-y-lam-i-n com pounds, amino-'aZo-benzene-disultonie acid,

iii-taro-a-mino-phenol-sulfonic acids, and the like. I

-My new coloring matters contain a residue co responding to the ormula where R is an aromatic esidue and are characterized by consisting when .dry of yellow. to brown powders which yield from orange to: yellow sohi-tions in concentrateil sulfuric acid, yield yellow to red lake of excellent Eastncss against the action of light,

Specification of Letters atent Application filed September 19, 1,911,

Patented oet. r, rare. Se i o- 659,216

and. on reduction with stannons chlorid and hydrochloric acid give rise to a negatively substituted amin.

.The following examples will serve to illustrate further the nature of my invention, which, however, is not confined to these examples. The parts are by weight. Example 1: 'Diazotize one hundred and seventy-two and one-halfparts ogt' 3-chl-or-finitranilin in the usual manner and allow the .diazo solution to run into a dilute, solution. .of one hundred and fifty parts of 1.3-

diketo-hydro-inden I which has been made acid with sulfuric acid and is maintained .at from zero to fine degrees centigrade.

ll' hen the combination is complete, filter ofl' th greenish yellow dye which is practically insoluble in water, alcohol and oil, and yields a greenish yellow lake of excellent fastness against the action of light.

Example 2: Diazotize one hundred and se\ 'enty-three parts of sulfanilic acid and introduce the suspension into a dilute solution containing one hundred and fifty parts .of 1.3-diketo-hydro-inden and two hundred and fifty parts of calcined soda, while main taining the le l lperature at from zero to five degrees centigrade. /V hen the combination is complete, salt out the coloring matter,

which consists of. a yellow powder which dyes wool from an acid bath greenish yellow shades. Its barium lake is brilliant greenish yellow.

Example 3: D-i-azotize two hundred and wenty-thine and onerhali parts of 4c-chlor- 2amii-io-phenol(i-sulfonic acid in the usual manner and introduce the suspension into an llqneous solution of one hundred and fifity parts-of 1,S-d iketWhydrQ-inden, which is maintained alkaline by means of sodium carbonate and the temperature of which lies between zero and five degrees centigrade. When the combination is complete, salt out the coloring matter, which consists of a brown powder and which dyes wool from an acid bath yellow, which shades, on treatment with bichromate, turn bordeaux,

Example 4:: Diazotize one hun dredand seventy-two and one-half parts of 3=ch-lor-.6- nitranilin and allow thesolution to run into an ice-cold solutionot' two hundred and fifty two parts of the disodium salt of 1.3- dikctohydno-inden-:Zcarboxylic acid, which has :been acidified with sulfuric acid.

first a light yellow precipitate is formed and later an intense greenish yellow precipitate, and at the same time carbon dioxid is evolved. Stir for, about eight hours and filter oil the coloring matter which gives rise to greenish yellow lakes of excellent fastness against the action of light. If, in this example, the disodium salt of 1.3-dilcetohydro-inden-2-carboxylic acid be replacedby an equivalent quantity of the sodium salt of the ethyl ester of 1.3diketo-hydro-inden- Q-carboxylic acid, a light yellow product is at first obtained which upon warming with alkili yields the free earboxylic acid, which upon treatment with acid gives the coloring matter.

Example 5: Diazotize one hundred and sixty-two parts of :lfi-dichlor-anilin in the usual manner and allow the solution to run into an aqueous solution of one hundred and forty-five parts. of 1.3--diketo-hydro-inden to zero to five degrees Centigrade. When the formula l In a manner similar to those described in the foregoing examples, other diazo compounds derived from negatively substituted amins and also derivatives of 1.3-diketohydro-inden can be employed.

The following table gives the properties which an excess of sodium acetate-has been of some of the coloring matters obtainable added and which is maintained at from according to my invention:

' Color of the Coloring matter from 1.3diketo-liydro-mdeii and Color of the direct the diaz o Compound [r Solution in water. Shade on wool. baiiumlgllinmium lake Oi'tho-nitranilin Insoluble... Yellow.

l-Chloi'Q-nitranilin .(lo Do.

8-Ch1or'6-nitranllin ...do Gi'eenish yellow.

3-Nitro-4-amino-tolucne ..do Orange-yellow.

2.4-Dinitranilin "do GlOenlSh yellow.

Metanilic acid Yellow Greci|ishyellow Yellow Sulfanilic acid ..do ..do GreenisliyeHow 3-Chlor-aniliii-4-sulfonlc acid ...,.(1o Yellow do l-Nap'lithylamiiil-sulfonic acid Orange Orange Red 2-Naphtliylamin-6-sulfoiiic acid ..(lo ..do Yellow-orange...

Amino-azo-henzene-disullonicacid 1o ..do Orange 4-Chlor-Z-amino-phenol-Gsulionicacid Bordeaux i'ed.... Yellow G-Nitrefl-amino-phenol-4-sultonic acid Pure red Red Now what I claim is,: body, which coloring matters contain a r'esi 1. The process of producing azo coloring due corresponding to the formula matter by combining a negatively substituted CO diazo compound with a 1.3-diketo-hydroinden body. (JHN=N-R 2. ihe piocess ol produc ng a o CQlOilng matter by (jmnlfllllii' (lllli lOtlfitl 2.'.)- licliloi'- v anilin with l. i-(lll((l()-liy(llO-lliklQIl. where R is an aromatic residue and Consist,

3. As new lll u-les ol manulm-lnre the mo I when (lry, of yellow to brown powders, yield coloring matters which can he btained by i lrom yellow to-orange solutions in concencombming a negatively suhsliluled (llilZO l'ral'eil sul'l'uric acid, yield yellow to red compound Wllh a 1.3-diketo-liydio-inden lakes of excellent iastness against the action nee/5,305

of light, and on reduction with stennous chlorid and hydrochloric acid give rise to a negatively substituted umin.

4-. As a new article of manufacture the 2120 coloring matter which can be obtained by (-onibii'nng diazotized. 2.5-dichlor-anilin with .lJ-Ldilreto-hydro-inden, which coloring m uter possesses a. constitution corresponding to the formula y consists, when dry, of a yellow powder,

yields an orange-red solution in concentrated sulfuric acid, yields a greenish yellow lake of excellent fastnes's against the action of light, and which upon reduction with 20 GTTO SCHMIDT.

Witnesses:

J. Ammo. LLoYD, JOSEPH HAEFFER. 

